Meta-phenylene-diamines

ABSTRACT

Novel meta phenylenediamines are provided having one or two particular benzyl radicals as substituents along with other optional substituents on the aromatic diamine ring and optionally substituents on the benzyl aromatic ring. 
     The diamines are sterically hindered and thereby have lower amine reactivity as compared with the unsubstituted diamines. 
     The diamines are useful as curing agents for epoxy resins and find particular utility as extenders in the formation of novel polyurethane-polyurea polymers.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of pending application Ser.No. 332,534 filed Dec. 12, 1981, hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to aromatic amines and is more particularlyconcerned with a novel class of alkylated meta-phenylenediamines.

2. Description of the Prior Art

Aromatic amines and particularly aromatic diamines are well known typesof compounds finding many applications in the chemical art. Typically,aromatic amines have found utility as starting materials andintermediates in the preparation of other products such as isocyanates,pharmaceuticals, various types of polymers, plastics, and the like. Someof the aromatic diamines find particular utility as curatives in variouspolymer systems.

Other known classes of aromatic diamines include, typically, theα,α'-bis(aminoaryl)xylenes disclosed in U.S. Pat. No. 3,424,795; thelimited number of nuclear alkylated aromatic amines and diaminesdisclosed in U.S. Pat. Nos. 3,678,112; 3,678,113 and 3,862,233; thealkylated toluenediamines and alkylated 4,4'-diaminodiphenylmethanesdisclosed in U.S. Pat. Nos. 3,428,610 and 4,218,543; certain meta- orpara-isopropenylphenylbenzyl derivatives of aromatic mono- and diaminesin German DS No. 17 686 97; and finally simple diamines such as thediaminodiphenylmethanes, toluenediamines, and the like.

I have now discovered a novel class of sterically hindered aromaticmeta-phenylene diamines which are easily obtained from readily availablestarting materials. Further, the aromatic diamines in accordance withthe present invention exhibit a wide range of amine basicity orreactivity depending on the extent of the steric hindrance which, inturn, depends on the extent of the substitution in the three possiblepositions ortho to the two amino groups on the aromatic ring.

Not only can the amine reactivity, i.e. amine basicity, be varieddepending on the substitution noted above but other important molecularproperties such as compound solubility and melting ranges can beinfluenced depending on the particular structure and/or isomer mixtureschosen.

The ability to influence amine basicity in the present diamines makesthem particularly useful as chain extenders in polyurethane-polyureapolymers which application will be discussed in detail below as part ofthe present invention.

SUMMARY OF THE INVENTION

This invention comprises m-phenylenediamines (I) having (a) at leastone, and not more than two, of the positions ortho to the amino groupssubstituted by a member selected from benzyl groups having the formulae:##STR1## wherein R₁ is selected from the class consisting of hydrogenand lower alkyl, R₂ is lower alkyl, C_(n) H_(2n) is alkylene having from2 to 5 carbon atoms in the chain, R is an inert substituent, n is aninteger from 0 to 5, m is an integer from 0 to 4; and (b) a memberselected from the group consisting of hydrogen and lower alkyl attachedto the nuclear carbon atoms ortho to the amino groups which do not carryone of said benzyl groups.

This invention also comprises m-phenylenediamines according to the abovedefinition which are additionally substituted by hydrocarbyl on thenuclear carbon atom which is in the meta position with respect to thetwo amino groups.

Preferred m-phenylenediamines (II) in accordance with the presentinvention have (a) at least one, and not more than two, of the positionsortho to the amino groups substituted by a benzyl group having theformula ##STR2## wherein R₁ and R₂ are as defined above; and (b) amember selected from the group consisting of hydrogen and lower alkylattached to the nuclear carbon atoms ortho to the amino groups which donot carry one of said benzyl groups.

This invention also comprises polyurethane-polyurea polymers prepared byreaction of an organic polyisocyanate, a polyol, and an extender whereinthe improvement comprises employing as the extender a m-phenylenediamineaccording to (I) above.

The term "lower alkyl" means alkyl having from 1 to 8 carbon atoms,inclusive, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl,octyl, and isomeric forms thereof.

The preferred lower alkyl radicals have 1 to 4 carbon atoms and are asdefined above.

The term "alkylene from 2 to 5 carbon atoms" means 1,2-ethylene,1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,2- and2,3-butylene, 1,5-pentylene, 1,4-pentylene, 1,2-, 2,3-, 1,3- and2,4-pentylene, and the like. Preferred alkylene is 1,2-ethylene.

The term "hydrocarbyl" means the monovalent radical obtained by removingone hydrogen atom from the parent hydrocarbon having from 1 to 18 carbonatoms. Illustrative of hydrocarbyl are alkyl such as methyl, ethyl,propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl,octadecyl, and the like, including isomeric forms thereof; alkenyl suchas vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl, decenyl,undecenyl, tridecenyl, hexadecenyl, octadecenyl, and the like, includingisomeric forms thereof; aralkyl such as benzyl, phenethyl, phenylpropyl,benzhydryl, naphthylmethyl, and the like; aryl such as phenyl, tolyl,xylyl, naphthyl, biphenylyl, and the like; cycloalkyl such ascyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo/o/ ctyl and thelike including isomeric forms thereof; and cycloalkenyl such ascyclopentenyl, cyclohexenyl, cycloheptenyl, cyclo/o/ ctenyl, and thelike, including isomeric forms thereof.

The hydrocarbyl groups can be substituted by one or a plurality ofsubstituents provided the latter are not reactive with amine groups.Illustrative of such substituents are halo, i.e. chloro, bromo, fluoroand iodo; nitro; alkoxy from 1 to 8 carbon atoms, inclusive, such asmethoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy,octyloxy and the like, including isomeric forms thereof; alkylmercaptofrom 1 to 8 carbon atoms, inclusive, such as methylmercapto,ethylmercapto, propylmercapto, butylmercapto, pentylmercapto,hexylmercapto, heptylmercapto, octylmercapto, and the like, includingisomeric forms thereof; and cyano.

A preferred class amongst the hydrocarbyl groups is the alkyl classdefined above and a preferred species is methyl.

The term "inert substituent" means any radical which does not react withthe amino groups and is inclusive of the hydrocarbyl groups which may ormay not be substituted by inert groups as defined above.

The preferred inert substituents are halogen with chlorine mostpreferred.

The diamines in accordance with the present invention are useful for allthe purposes set forth above for the prior art aromatic diamines butthey find utility as curatives for polymer systems such as epoxy resincuratives and find particular utility as extenders in polyurethanes.

DETAILED DESCRIPTION OF THE INVENTION

Generally speaking, the aromatic diamines in accordance with theinvention are crystalline solids. Depending upon the extent and type ofsubstitution on the aromatic ring, the diamines can range from low tohigh melting solids, for example, having melting points from about 80°C. or lower, to a high of about 240° C. or higher with valuesintermediate therebetween. However, some diamines are liquids or oilseven when in a pure state.

The aromatic diamines in accordance with the present invention arefurther characterized by having, for the most part, good solubility incommon organic solvents such as ketones, alcohols, ethers, esters,chlorinated hydrocarbon solvents, dipolar aprotic solvents, and thelike. Generally speaking, compound solubility can be increased byemploying isomer mixtures of the diamines of formula (I).

In a surprising, and advantageous, feature of the aromatic diamines inaccordance with the present invention, their reactivities as measured bytheir relative reactivities with phenyl isocyanate, can cover arelatively broad range depending on the type and extent of substitutionon the aromatic diamine ring. In the test procedure, the subject diamineis reacted with a stoichiometric amount of phenyl isocyanate at a dilutereactant concentration level (for example about 6.8 weight percent) in asolvent (for example dimethylacetamide) at ambient room temperature(about 20° C.) under Argon and the disappearance of the isocyanate band(2250 cm⁻¹) in the infrared is followed on aliquot samples.

Illustratively, 5-(α,α-dimethylbenzyl)-2,4-toluenediamine in accordancewith the present invention is characterized by a reactivityapproximately equal to MOCA or approximately 1/150 of4,4'-methylenebis(aniline).3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamine in accordance with thepresent invention is approximately 1/3 of MOCA in reactivity.

Therefore, the aromatic diamines in accordance with the presentinvention can provide a range of basic reactivities depending on theapplication in which they are being employed.

Illustrative, but not limiting, of the aromatic diamines in accordancewith the present invention are 4-(α-methylbenzyl)-m-phenylenediamine,4-(α-methyl-p-methylbenzyl)-m-phenylenediamine,4-(α-methyl-p-ethylbenzyl)-m-phenylenediamine,4-(α-methyl-p-propylbenzyl)-m-phenylenediamine,4-(α-methyl-p-butylbenzyl)-m-phenylenediamine,4-(α-methyl-p-amylbenzyl)-m-phenylenediamine,4-(α-methyl-p-hexylbenzyl)-m-phenylenediamine,4-(α-methyl-p-heptylbenzyl)-m-phenylenediamine,4-(α-methyl-p-octylbenzyl)-m-phenylenediamine,4-(α-methyl-p-nonylbenzyl)-m-phenylenediamine,4-(α-methyl-p-decylbenzyl)-m-phenylenediamine,4-(α-methyl-p-octadecylbenzyl)-m-phenylenediamine,4-(α-methyl-p-isopropylbenzyl)-m-phenylenediamine,4-(α-methyl-p-isobutylbenzyl)-m-phenylenediamine,4-(α-methyl-p-2-ethylhexylbenzyl)-m-phenylenediamine,4-(α-methyl-p-isononylbenzyl)-m-phenylenediamine,4-(α-methyl-p-chlorobenzyl)-m-phenylenediamine, 4-(60-methyl-p-bromobenzyl)-m-phenylenediamine,4-(α-methyl-p-methoxybenzyl)-m-phenylenediamine,4-(α-methyl-p-benzylbenzyl)-m-phenylenediamine,4-(α-methyl-p-phenethylbenzyl)-m-phenylenediamine,4-(α-methyl-p-phenylbenzyl)-m-phenylenediamine,4-(α-methyl-p-tolylbenzyl)-m-phenylenediamine,4-(α-methyl-p-allylbenzyl)-m-phenylenediamine,4-(α-methyl-p-cyclobutylbenzyl)-m-phenylenediamine,4-(α-methyl-p-cyclopentylbenzyl)-m-phenylenediamine,4-(α-methyl-p-cyclohexylbenzyl)-m-phenylenediamine,4-(α-methyl-p-cycloheptylbenzyl)-m-phenylenediamine,4-(α-methyl-p-cyclooctylbenzyl)-m-phenylenediamine,4-[α-methyl-p-(1-cyclopentenyl)benzyl]-m-phenylenediamine,4-[α-methyl-p-(1-cyclohexenyl)benzyl]-m-phenylenediamine, and the like;4-(α-ethylbenzyl)-m-phenylenediamine,4-(α-propylbenzyl)-m-phenylenediamine,4-(α-butylbenzyl)-m-phenylenediamine,4-(α-amylbenzyl)-m-phenylenediamine,4-(α-hexylbenzyl)-m-phenylenediamine,4-(α-heptylbenzyl)-m-phenylenediamine,4-(α-octylbenzyl)-m-phenylenediamine,4-(α-ethyl-2,4-dimethylbenzyl)-m-phenylenediamine,4-(α,α-dimethylbenzyl)-m-phenylenediamine,4-(α,α-diethylbenzyl)-m-phenylenediamine,4-(α-methyl-α-propylbenzyl)-m-phenylenediamine,4-(1-benzocyclopentyl)-m-phenylenediamine,4-(1-benzocyclohexyl)-m-phenylenediamine,4-(1-benzocycloheptyl)-m-phenylenediamine,4-(1-benzocyclooctyl)-m-phenylenediamine,4-[1-(1-methylbenzocyclopentyl)]-m-phenylenediamine,4-(α,α-dimethylbenzyl)-5-methyl-m-phenylenediamine,4-(α,α-dimethylbenzyl)-5-ethyl-m-phenylenediamine,4-(α,α-dimethylbenzyl)-5-methoxy-m-phenylenediamine,4-(α,α-dimethylbenzyl)-5-allyl-m-phenylenediamine, and the like;4,6-bis(α-methylbenzyl)-m-phenylenediamine,4,6-bis(α-methyl-p-methylbenzyl)-m-phenylenediamine,4,6-bis(α,α-dimethylbenzyl)-m-phenylenediamine,4,6-bis(α,α-dimethylbenzyl)-5-methoxy-m-phenylenediamine, and the like;5-(α-methylbenzyl)-2,4-toluenediamine,5-(α-methyl-p-tolylbenzyl)-2,4-toluenediamine,5-(α-methyl-p-ethylbenzyl)-2,4-toluenediamine,5-(α-methyl-p-chlorobenzyl-2,4-toluenediamine,4-(α-methylbenzyl)-6-ethyl-m-phenylenediamine,4-(α-methylbenzyl)-6-butyl-m-phenylenediamine,4-(α-methylbenzyl)-6-octyl-m-phenylenediamine,5-(α,α-dimethylbenzyl)-2,4-toluenediamine,5-(α,α-diethylbenzyl)-2,4-toluenediamine,5-(α,α-dimethyl-p-tolylbenzyl)-2,4-toluenediamine,5-(α-ethylbenzyl)-2,4-toluenediamine,5-(α,α-dimethyl-p-chlorobenzyl)-2,4-toluenediamine,5-(α,α-dimethyl-p-phenethylbenzyl)-2,4-toluenediamine,5-(1-benzocyclopentyl)-2,4-toluenediamine,5-(1-benzocyclohexyl)-2,4-toluenediamine,5-(α,α-dimethylbenzyl)-6-methyl-2,4-toluenediamine,5-(α,α-dimethylbenzyl)-6-ethyl-2,4-toluenediamine,5-(α,α-dimethylbenzyl)-6-allyl-2,4-toluenediamine,5-(α,α-dimethylbenzyl)-6-methoxy-2,4-toluenediamine,3,5-bis(1-benzocyclopentyl)-2,4-toluenediamine,3-(1-benzocyclopentyl)-2,4-toluenediamine,3-(α-methylbenzyl)-2,4-toluenediamine,3-(α,α-dimethylbenzyl)-2,4-toluenediamine,3-(α,α-dimethyl-p-chlorobenzyl)-2,4-toluenediamine,3-(α,α-dimethyl-4-methoxybenzyl)-2,4-toluenediamine, and the like;3-(α-methylbenzyl)-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-4-methyl-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-4-ethyl-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-4-allyl-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-4-methoxy-2,6-toluenediamine,3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamine,3,5-bis(α,α-dimethylbenzyl)-4-methoxy-2,6-toluenediamine,3-(α-methyl-α-ethylbenzyl)-2,6-toluenediamine,3-(α-methyl-α-butylbenzyl)-2,6-toluenediamine,3-(α,α-dimethyl-p-tolylbenzyl)-2,6-toluenediamine,3-(α,α-dimethyl-p-chlorobenzyl)-2,6-toluenediamine,3-(1-benzocyclopentyl)-2,6-toluenediamine,3-(1-benzocyclohexyl)-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-5-methyl-2,6-toluenediamine,4-(α,α-dimethylbenzyl)-2-ethyl-m-phenylenediamine,4-(α,α-dimethylbenzyl)-2-butyl-m-phenylenediamine,4-(α,α-dimethylbenzyl)-2-octyl-m-phenylenediamine, and the like.

Preferred amongst the aromatic diamines set forth above are those havingeither the 2,4-, or 2,6-toluene-diamine nucleus, and most preferredwithin each of those two groups are those having the α,α-dimethylbenzylsubstituent group on said toluenediamine nucleus.

Particularly preferred are the diamine mixtures comprising (a) fromabout 70 to about 95 percent by weight of5-(α,α-dimethylbenzyl)-2,4-toluenediamine and (b) the remaining 30 to 5percent by weight being 3-(α,α-dimethylbenzyl)-2,6-toluenediamine basedon the combined weights of (a) and (b).

The aromatic diamines (I) in accordance with the present invention arereadily prepared by alkylating the appropriately substituted aromaticdiamines (III) with an appropriate styrene compound (IVa) or precursorthereof (discussed in detail below) or an appropriate benzocycloalkenecompound (IVb) according to the following schematic equation ##STR3##wherein X is hydrogen or hydrocarbyl, R, R₁, m and n are defined asabove, R₃ is hydrogen or lower alkyl, C_(n) H_(2n) is alkylene having 1to 4 carbon atoms similar to alkylene defined above but having thesmaller carbon atoms range; and the alkylidene (R₃ CH═) andcycloalkylidene (C_(n) H_(2n) CH═) of (IVa) and (IVb) become the R₂ andthe C_(n) H_(2n) respectively of the m-phenylenediamines (I) definedabove.

Generally speaking, the alkylation is carried out conveniently byheating the reactants in the appropriate proportions in the presence ofa catalyst until the desired compound (I) is formed. For typicalreaction methods and conditions see the art cited supra, particularly DSNo. 1768697, and see also U.S. Pat. No. 4,008,275 for typical catalysts.

Optionally, an inert organic solvent may be employed such aschlorobenzene, dichlorobenzene, nitrobenzene, and the like, and theresulting mixture or solution is brought into contact with the catalystand the mixture stirred at the appropriate temperature.

Alternatively, and in a preferred embodiment, no organic solvent isemployed but rather an excess of one reactant over the other is used.The reaction of (III) with (IVa) and (IVb) is an equilibrium process andby using an excess of one reactant the dual purpose of a solvent effectand the shifting of the reaction equilibrium toward higher conversionsis achieved.

It will be readily understood by those skilled in the art that thechoice of which reactant to use in excess to achieve the maximum yieldof desired product (I) can readily be determined by trial and error byone skilled in the art.

Advantageously, the molar proportions of (IVa) or (IVb) to diamine (III)can fall within the ratios of about 20/1 to 1/20, preferably about 10/1to 1/10. In a preferred mode of preparation, the (IVa) or (IVb) is usedin a molar excess over (III) of about 10/1 to about 5/1.

Since compounds in accordance with the present invention can have two ofthe benzyl radicals arising from the double alkylation of the startingamine, such dialkylated products can be prepared in either a one-stepreaction, wherein both alkylations take place in the one procedure, or,alternatively, in a two-step procedure wherein the first monoalkylatedcompound is formed and then alkylated in a second step to introduce thesecond benzyl radical.

Ordinarily, the alkylation is carried out at elevated temperatures,advantageously within a range of from about 40° C. to about 250° C.

The reaction mixture is preferably stirred with the catalyst componentin any suitable reaction vessel, preferably, under an inert atmospheresuch as nitrogen or argon at a temperature falling within the aboverange. Heating is continued until routine analytical procedures, carriedout on an aliquot, indicate that reaction is substantially complete.

Illustrative of such analytical procedures are high pressure liquidchromatography (HPLC) to determine weight percent of components in themixture, nuclear magnetic resonance (Nmr) and infrared spectroscopy, andthe like.

Any convenient alkylation catalyst used for aromatic amine alkylationcan be employed. Typically useful are the aqueous mineral acids, clays,acid clays, diatomaceous earths, zeolites, aromatic sulfonic acids andthe salts formed between the starting diamines (III) and said aromaticsulfonic acids, and the like. For a discussion on such catalysts seeU.S. Pat. No. 4,008,275 whose disclosure in respect thereof is herebyincorporated by reference.

A preferred group of catalysts for the preparation of the aromaticdiamines (I) include the natural and synthetic zeolites and aromaticsulfonic acids and the salts formed between the starting diamines (III)and said aromatic sulfonic acids.

Generally speaking the catalyst is employed within a range of from about5 weight percent to about 95 weight percent based on the combined weightof diamine and catalyst.

Illustrative of the diamines (III) which may be employed arem-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine,4-ethyl-m-phenylenediamine, 4-propyl-m-phenylenediamine,4-butyl-m-phenylenediamine, 4-octyl-m-phenylenediamine,5-methyl-m-phenylenediamine, 5-ethyl-m-phenylenediamine,5-propyl-m-phenylenediamine, 5-butyl-m-phenylenediamine,5-octyl-m-phenylenediamine, 5-methoxy-m-phenylenediamine,5-allyl-m-phenylenediamine, 5-phenyl-m-phenylenediamine,5-benzyl-m-phenylenediamine, 5-cyclohexyl-m-phenylenediamine,2-ethyl-m-phenylenediamine, 2-butyl-m-phenylenediamine,2-octyl-m-phenylenediamine, 6-methyl-2,4-toluenediamine,6-ethyl-2,4-toluenediamine, 6-allyl-2,4-toluenediamine,6-methoxy-2,4-toluenediamine, 6-phenyl-2,4-toluenediamine,6-benzyl-2,4-toluenediamine, 6-cyclohexyl-2,4-toluenediamine,4-methyl-2,6-toluenediamine, 4-ethyl-2,6-toluenediamine,4-allyl-2,6-toluenediamine, 4-methoxy-2,6-toluenediamine,4-phenyl-2,6-toluenediamine, 4-benzyl-2,6-toluenediamine,4-cyclohexyl-2,6-toluenediamine, and the like.

Preferred starting diamines are the 2,4- and 2,6-toluenediamines.Particularly preferred are the mixtures comprising from about 60 to 85percent by weight of 2,4-toluenediamine and 40 to 15 percent by weightbeing 2,6-toluenediamine.

Illustrative of the styrenes which can be employed in the preparation ofthe compounds of the invention are styrene itself, p-methylstyrene,p-ethylstyrene, p-propylstyrene, p-butylstyrene, p-amylstyrene,p-hexylstyrene, p-heptylstyrene, p-octylstyrene, p-nonylstyrene,p-decylstyrene, p-octadecylstyrene, p-isopropylstyrene,p-isobutylstyrene, p-2-ethylhexylstyrene, p-isononylstyrene,p-chlorostyrene, p-bromostyrene, p-methoxystyrene, p-benzylstyrene,p-phenethylstyrene, p-phenylstyrene, p-tolylstyrene, p-allylstyrene,p-cyclobutylstyrene, p-cyclopentylstyrene, p-cyclohexylstyrene,p-cycloheptylstyrene, p-cyclooctylstyrene, p-(1-cyclopentenyl)styrene,p-(1-cyclohexenyl)styrene, and the like; β-methylstyrene,β-ethylstyrene, β-propylstyrene, β-butylstyrene, β-pentylstyrene,β-hexylstyrene, β-heptylstyrene, β-methyl-2,4-dimethylstyrene, and thelike; α-methylstyrene, α-ethyl-β-methylstyrene, α-methyl-β-ethylstyrene,indene, benzocyclohexene-1, benzocycloheptene-1, benzocyclooctene-1,1-methyl-indene, α-methyl-p-chlorostyrene, α-methyl-p-bromostyrene,α-methyl-p-tolylstyrene, α-methyl-p-ethylstyrene,α-methyl-p-butylstyrene, α-methyl-p-benzylstyrene,α-methyl-p-allylstyrene, α-methyl-p-cyclopentylstyrene, and the like.

In addition to employing the styrenes per se in the preparation ofaromatic diamines in accordance with the present invention it ispossible to form said compounds in situ by introducing a precursor ofany of said compounds which will generate the styrene under theconditions prevailing in the reaction mixture. For example, dimers,trimers, and higher oligomeric forms which will revert to the styrenesunder the elevated temperatures and acid conditions of the abovedescribed preparation of (I) can be employed therein. Further, thevarious aryl substituted carbinols such as phenylisopropyl alcohol whichon dehydration will provide the appropriate styrene compound can beemployed to prepare the compounds of formula (I).

The starting aromatic diamines and styrenes are well known in the art asare the carbinols or oligomeric styrene materials.

As set forth above, the substituted aromatic amines of the inventionfind particular utility as extenders for the preparation of polyurethanepolyureas. The polyurethane-polyurea polymers extended by the diamineshaving formula (I) can be formed as cellular, microcellular, or solidpolyurethane-polyurea polymers using any of the prior art methods knownto those skilled in the art; see Polyurethanes: Chemistry and TechnologyII, by J. H. Saunders and K. C. Frisch, 1964, Interscience Publishers,New York, N.Y., for teaching of the preparation of polyurethanes.

In a preferred embodiment of the present invention thepolyurethane-polyurea polymers employing the diamines (I) as extendersare prepared as molded materials, particularly reaction injection moldedpolyurethane-polyureas; for typical lists of reactants and procedureswhich can be used in combination with the diamines (I) to produce thepolyurethane-polyureas see U.S. Pat. No. 4,296,212 whose disclosure isincorporated by reference herein.

The following examples describe the manner and process of making andusing the invention and set forth the best mode contemplated by theinventors of carrying out the invention but are not to be construed aslimiting.

EXAMPLE 1

A 100 ml. reaction flask was equipped with a stirrer, thermometer, andreflux condenser. The flask was charged with 29.5 g. (0.25 mole) ofα-methylstyrene, 6.48 g. (0.06 mole) of m-phenylene diamine, 7.24 g.(0.04 mole) of m-phenylene diamine dihydrochloride, and 20 ml. of water.The mixture was heated at reflux at 95°-100° C. for 24 hours.

The solution was allowed to cool and mixed with 140 ml. of 1.0Nhydrochloric acid. The aqueous solution was washed in a separatoryfunnel 3× with 50 ml. portions each of methylene chloride in order toremove the excess α-methylstyrene. The resulting aqueous fraction wasmade slightly basic by the addition of the appropriate amount of 10Nsodium hydroxide. An oil separated which was extracted with 2×40 ml.portions each of methylene chloride.

The combined methylene chloride fractions were washed with 3×50 ml.portions each of warm water to remove unreacted phenylene diamine.Concentration of the organic layer in vacuum resulted in a solidresidue. Vacuum distillation of this residue provided a pale yellowdistillate, b.p. 168°-176° C. (0.05 mm pressure of mercury; wt.=7.8 g.(62%) of 4-(α,α-dimethylbenzyl)-1,3-phenylene diamine having thefollowing formula ##STR4## in accordance with the present invention.

The distillate solidified on standing at room temperature and wasrecrystallized from toluene to afford colorless crystals, m.p. 83°-83.5°C. Nuclear magnetic resonance (Nmr) confirmed the structure along withthe following elemental analysis.

Calcd. for C₁₅ H₁₈ N₂ : C, 79.60%; H, 8.02%; N, 12.38%; Found: C,79.63%; H, 8.10%; N, 12.42%.

High pressure liquid chromatography (HPLC) of the original solid residueproduct prior to vacuum distillation showed the presence of a smallamount of a dibenzylated product which product was later prepared in aseparate experiment described below.

EXAMPLE 2

A 250 ml. reaction flask equipped with a stirrer, thermometer, refluxcondenser and gas outlet tube which was connected to a receiving flaskcooled by a cold water bath was charged with 70.8 g. (0.6 mole) ofα-methylstyrene, 10.8 g. (0.1 mole) of m-phenylene diamine, and 10 g. ofZeolite XZ-25 100-150 mesh untreated (supplied by W. R. Grace ChemicalCo., Baltimore, Md. Under a slow stream of nitrogen and with rapidstirring, the flask contents were heated. Initially, a small amount ofwater (from the Zeolite) was co-distilled from the flask with someα-methylstyrene and was collected in the receiving flask. Followingthis, the nitrogen flow was stopped and the mixture was heated at about165° C. for 24 hours.

The reaction mixture while still hot was filtered by pouring it througha heated Buchner funnel to remove the Zeolite. Upon cooling to roomtemperature, a crystalline precipitate separated from the filtrate. Theprecipitate was collected by suction filtration to provide 17.2 g. of amixture of predominantly the dibenzylated product4,6-bis(α,α-dimethylbenzyl)-1,3-phenylene diamine in accordance with##STR5## the present invention and a minor amount of the monobenzylateddiamine described in Example 1.

Pure dibenzylated product was obtained as colorless crystals byrecrystallizing the crude crystalline material twice from toluene.Additional product was isolated by washing the Zeolite catalyst severaltimes with methylene dichloride, combining the methylene dichloridewashings with the first filtrate from the reaction mixture and removingthe solvent and unreacted α-methylstyrene by distillation to provide aresidue, and, finally, treatment with chloroform. Total yield of theisolated dibenzyl product was 58%; m.p. 236°-237° C.; insoluble inethanol, acetone, ethylene glycol, soluble in methylene dichloride,diethylene glycol dimethyl ether (diglyme), and hot toluene; Nmrconfirmed the structure along with the following elemental analysis.

Calcd. for C₂₄ H₂₈ N₂ : C, 83.67%; H, 8.19%; N, 8.13%; Found: C, 83.28%;H, 8.37%; N, 8.14%.

Thin layer chromatography (TLC) experiments as well as HPLC analysis onthe residue above prior to treatment with chloroform indicated thepresence of additional dibenzylated product, the monobenzylated compoundof Example 1, unreacted phenylene diamine, a component believed to bepolymeric α-methylstyrene and a trace of N-benzylated material.

EXAMPLE 3

A reaction flask equipped as set forth in Example 2 was charged with2.26 g. (0.01 mole) of 4-(α,α-dimethylbenzyl)-1,3-phenylene diamine,11.8 g. (0.1 mole) of α-methylstyrene, and 2.0 g. of Zeolite XZ-25.

Using the same procedure as set forth in Example 2, heating of themixture was commenced. After 4 hours at 160°-165° C. the reactionmixture was analyzed by HPLC and TLC and shown to contain4,6-bis(α,α-dimethylbenzyl)-1,3-phenylene diamine as the major componentalong with a minor amount of the starting4-(α,α-dimethylbenzyl)-1,3-phenylene diamine plus a trace of m-phenylenediamine and a trace of poly α-methylstyrene.

The reaction mixture was treated according to the work-up procedure setforth in Example 2 to afford 2.1 g. (61%) of4,6-bis(α,α-dimethylbenzyl)-1,3-phenylene diamine in accordance with thepresent invention.

EXAMPLE 4

A 250 ml. reaction flask equipped according to Example 2 was chargedwith 12.2 g. (0.1 mole) of 2,4-toluenediamine, 59 g. (0.5 mole) ofα-methylstyrene, and 10 g. of Zeolite XZ-25.

Using the same procedure outlined in Example 2, the rapidly stirredmixture was heated for 20 hours at 160° C. HPLC analysis indicated thatconversion of the 2,4-toluenediamine was at least 87%. The hot reactionmixture was filtered through a heated Buchner funnel. The collectedZeolite was washed 3× with 20 ml. portions each of methylene chloride.The filtrate and washings were combined and the solvent removed undervacuum leaving a residue. The residue was distilled under vacuum througha simple distillation head first at moderate vacuum to removeα-methylstyrene, i.e. b.p. 110° C. (23 mm. of mercury), then at highervacuum to collect the following fractions: 1. b.p. 145°-165° C. (0.05mm.), wt.=1.6 g. of unreacted 2,4-toluenediamine; 2. b.p. 165°-173° C.(0.05 mm.), wt.=19.0 g. of 5-(α,α-dimethylbenzyl)-2,4-diaminotoluene; 3.b.p. 173°-185° C. (0.05 mm., wt.= 2.8 g. of5-(α,α-dimethylbenzyl)-2,4-diaminotoluene and two other components whichwere separated by TLC and believed to be N-alkylated-2,4-toluenediamineand polymerized α-methylstyrene; 4. residue, wt.=1.3 g. of a mixture ofthe same component comprising fraction 3.

The fraction 2 was fractionated through a 12 cm. Vigreux column under avacuum of 0.07 mm. of mercury and using a heating bath temperaturestarting at about 230° C. and progressing up to about 250° C. to yieldthe following fractions: 2-1. b.p. up to 168° C., wt.=0.7 g.; 2-2. b.p.168°-176° C., wt.=4.9 g.; 2-3. b.p. 176°-177° C., wt.=8.3 g. pale yellowoil; 2-4. b.p. 177°-172° C., wt.=2.0 g.; residue, wt.=1.0 g. light brownliquid. The major fraction which solidified was5-(α,α-dimethylbenzyl)-2,4-toluenediamine ##STR6## in accordance withthe present invention. The crystalline product was found to be verysoluble in standard organic solvents including ethylene glycol. It stillcontained a trace of impurity. The impurity was removed by washing thecrystals with low boiling (35°-60° C.) petroleum ether. The product wasfurther recrystallized from a mixture of hot toluene and petroleum etherto provide colorless crystals; m.p. 90.0°-91.5° C. Total weight ofproduct isolated from both fractions 2 and 2 was 19.7 g. (82%). Nmrconfirmed the structure along with the following elemental analysis.

Calcd. for C₁₆ H₂₀ N₂ : C, 79.95%; H, 8.39%; N, 11.66%; Found: C,79.80%; H, 8.45%; N, 11.62%.

EXAMPLE 5

The apparatus described in Example 4 was charged with 12.2 g. (0.1 mole)of 2,6-toluenediamine, 59 g. (0.5 mole) of α-methylstyrene, and 10 g. ofZeolite XZ-25.

The reaction mixture was heated in accordance with the procedure setforth in Example 4 at a temperature of about 160° C. After 8 hours thereaction appeared to have reached equilibrium as evidenced by theconstancy of the product distribution determined from HPLC analysis ofaliquots of the reaction mixture. However, heating was continued for atotal of 20 hours so as to have equal reaction conditions with Example4.

The hot reaction mixture was filtered through a heated Buchner funnel.The collected Zeolite was washed with 3×20 ml. portions of methylenedichloride and the washings concentrated under vacuum to leave aresidue. The latter residue was combined with the filtrate obtainedabove which upon standing at room temperature had deposited acrystalline precipitate. After standing overnight the crystallineprecipitate was collected by suction filtration to provide 18.6 g. ofcolorless crystals which were recrystallized from a combination of hotmethanol and petroleum ether (b.p. 35°-60° C.) to provide largecolorless prisms; m.p. 191°-192° C.; soluble in common organic solvents(i.e., acetone, ethanol, etc.) and soluble in ethylene glycol at 100° C.(at least to the extent of 3 to 5% by wt. in ethylene glycol). Nmr andthe following elemental analysis confirmed the compound to be3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamine in accordance with thepresent invention. ##STR7##

Calcd. for C₂₅ H₃₀ N₂ : C, 83.75%; H, 8.43%; N, 7.82%; Found: C, 83.86%;H, 8.61%; N, 7.18%.

The filtrate remaining after removal of the above dibenzylated productwas distilled until the boiling point of the distillate reached 110° C.under 23 mm. of mercury pressure in order to remove α-methylstyrene. Theresidue was further distilled through a 5 cm. empty column under highvacuum (0.04 mm.) and the following fractions were collected: 1. b.p.147°-158° C., wt.=0.7 g.; 2. b.p. 158°-162° C., wt.=0.5 g.; 3. b.p.162°-164° C., wt.=3.5 g.; 4. b.p. 164°-170° C., wt.=1.6 g.; residue,wt.=1.0 g. Fraction 1 was essentially pure 2,6-toluenediamine. Fractions2 to 4 were essentially pure 3-(α,α-dimethylbenzyl)-2,6-toluenediaminehaving the formula ##STR8## in accordance with the present invention.

Fractions 2 to 4 were recrystallized from a combination of hot carbontetrachloride and petroleum ether (b.p. 35°-60° C.) to give colorlesscrystals, m.p. 113°-114° C. The structure of this product was confirmedby Nmr and the following elemental analysis.

Calcd. for C₁₆ H₂₀ N₂ : C, 79.95%; H, 8.39%; N, 11.66%; Found: C,79.89%; H, 8.16%; N, 11.73%.

The product yields from this reaction were 23.3% of the monobenzylatedmaterial, 54.7% of the dibenzylated material and 6% of the starting2,6-toluenediamine. A trace of an α-methylstyrene polymer was alsoobtained in the distillation residue.

Repetition of the above reaction but on a larger scale of startingmaterials and at 170° C. for 20 hours resulted in a 59% conversion ofthe starting diamine to form a 56.1% yield of the dibenzylated productand 36.5% yield of the monobenzylated product based on the converteddiamine.

EXAMPLE 6

Using the apparatus and procedure described in previous examples, areaction flask was charged with 36.6 g. (0.3 mole) of2,4-toluenediamine, 15.3 g. (0.1 mole) of p-chloroisopropenyl benzene,and 10 g. of Zeolite XZ-25 (predried at 400° C. for 3 hours). Themixture was stirred and heated at 200° C. for 24 hours under nitrogen.

After filtration of the reaction mixture, and removal of solvent(methylene chloride) and excess diaminotoluene, the product mixture wasdistilled under high vacuum (0.07 to 0.05 mm. of mercury). The followingsix fractions were collected and analyzed by Nmr: 1. b.p. 50°-52° C.,wt.=1.29 g. of p-chloroisopropenyl benzene; 2. b.p. 140°-175° C.,wt.=1.1 g. of 2,4-toluenediamine plus an unknown; 3. b.p. 175°-192° C.,wt.=2.0 g. of 5-(α,α-dimethyl-p-chlorobenzyl)-2,4-toluenediamine plus asmall amount of unknown impurity; 4. b.p. 192°-200° C., and 5. b.p.200°-204° C., both 4. and 5. together wt.=6.8 g. of crude5-(α,α-dimethyl-p-chlorobenzyl)-2,4-toluenediamine; 6.) b.p. 204°-218°C., wt.=1.8 g. predominantly5-(α,α-dimethyl-p-chlorobenzyl)-2,4-toluenediamine plus a small amountof unknown impurity; residue wt.=4.1 g. of tar.

Combined fractions 4 and 5 were further purified firstly by columnchromatography by eluting the product from the column using acombination of petroleum ether and methylene chloride (75/25) andcollecting it in column chromatography fractions 7, 8, and 9.

Secondly, the eluted product was distilled b.p. 194°-196° C. (0.05 mm.)to provide a light yellow glass, wt. 10.5 g. (38%). The hydrochloridesalt of the product was prepared for further purification by dissolvingthe amine in ether and passing in dry hydrogen chloride gas untilprecipitation of hydrochloride ceases. The salt was isolated byfiltration, recrystallized once from a mixture of methylene chloride andether, and recrystallized once from a mixture of methanol and ether. Alight yellow colored hydrochloride salt was obtained which wascharacterized by a double melting point, 184°-188° C. and 210°-214° C.

Upon neutralizing in aqueous solution of the hydrochloride, the freebase was obtained which was extracted from the aqueous mixture using 100ml. of methylene chloride solvent. The solvent was dried over magnesiumsulfate and then taken to dryness. Thus there was obtained pure5-(α,α-dimethyl-p-chlorobenzyl)-2,4-toluenediamine having the followingstructure in accordance with the present invention and whose structure##STR9## was confirmed by Nmr and the following elemental analysis.

Calcd. for C₁₆ H₁₉ N₂ Cl: C, 69.93%; H, 6.97%; N, 10.20%; Cl, 12.90%.Found: C, 69.86%; H, 6.24%; N, 10.15%; Cl, 13.02%.

EXAMPLE 7

Using the same apparatus described in the previous examples except thatthe reaction flask was additionally equipped with an addition funnel,the following experiment was carried out.

The flask was charged with 61.0 g. (0.5 mole) of 2,4-toluenediamine, and10.0 g. of Zeolite XZ-25 catalyst. The mixture was heated to 200° C.with rapid stirring under the positive flow of nitrogen. Over a 4 hourperiod under the above conditions, 4.17 g. (0.04 mole) of styrene wasadded slowly through the addition funnel to the reaction flask. Heatingand stirring was continued for another 4 hour period after the styreneaddition was completed. A small amount of styrene still remainedrefluxing at the end of the 8 hours.

The mixture was cooled to room temperature and treated with 50 ml. ofmethylene chloride. The catalyst was removed by filtration and to thefiltrate was added 100 ml. of petroleum ether (b.p. 35°-60° C.) toprecipitate the excess 2,4-toluenediamine which latter was also removedby filtration. The methylene chloride/petroleum ether filtrate waswashed 3× with 100 ml. portions each of water. Solvent was stripped fromthe organic layer under vacuum leaving a residue which was distilledunder 0.05 mm. pressure of mercury and the following fractions collectedand identified by Nmr analysis: 1. b.p. 138°-165° C., wt.=0.3 g. of2,4-toluenediamine; 2. b.p. 165°-170° C.; 3. b.p. 170°-180° C.,combination of fraction 2 and 3 is 4.9 g. of light yellow oil; 4. b.p.180°-183° C., wt.=0.70 g. of 5-(α-methylbenzyl)-2,4-toluenediamine;residue wt.=0.63 g.

The combination of fractions 2 and 3 was subjected to chromatographicseparation on a 1"×12" column of silica gel. The following numberedfractions were the ones found to contain product after the solvent wasremoved and analyzed by Nmr with the eluting solvent noted inparenthesis.

Chromatographic column fraction 1 (petroleum ether), small amount ofstyrene; chromatographic column fraction 8 (petroleum ether/methylenechloride 85/15), 3-(α-methylbenzyl)-2,4-toluenediamine; chromatographiccolumn fractions 9 to 15 inclusive (petroleum ether/methylene chloride80/20), a mixture of 3-(α-methylbenzyl)-2,4-toluenediamine, along withthe two N-benzylated side-products; chromatographic column fractions 17to 24, inclusive (petroleum ether/methylene chloride 3/2), wt.=2.5 g. ofpure 5-(α-methylbenzyl)-2,4-toluenediamine.

The latter product crystallized slowly and was eventually recrystallizedfrom a combination of hot toluene and petroleum ether, m.p. 103°-103.5°C. pale yellow needles, total weight of this product was 3.1 g. (34%).Nmr and the following elemental analysis confirmed the followingstructure in accordance with the present invention ##STR10##

Calcd. for C₁₅ H₁₈ N₂ : C, 79.60%; H, 8.02%; N, 12.38%; Found: C,79.59%; H, 7.97%; N, 12.30%.

The 3-(α-methylbenzyl)-2,4-toluenediamine obtained from chromatographiccolumn fraction 8 remained an oil and was distilled again, b.p.170°-174° C. (0.05 mm.) and formed a minor product with a yield of about5%. The Nmr analysis confirmed the following structure in accordancewith the present invention. ##STR11##

EXAMPLE 8

The apparatus described in Example 4 was charged with 12.2 g. (0.1 mole)of 2,4-toluenediamine, 58.0 g. (0.5 mole) of indene (practicalgrade >90% purity, supplied by Aldrich Chem. Co., Milwaukee, Wis.), and10 g. of Zeolite XZ-25.

The mixture was stirred and heated under nitrogen according to theprocedure set forth in Example 4, first at 160° C. for 16 hours but thentemperature was increased to 185° C. and heating continued thereat foranother 7 hours. During this heating moisture was distilled off from thecatalyst.

On conclusion of the heating the reaction mixture was filtered hotthrough a heated Buchner funnel to remove catalyst. The filtrate wasfirst distilled to remove the excess indene; b.p. 40° C. (0.05 mm.pressure of mercury), wt.=33.5 g. of indene. The residue was thenfractionated through a 5 cm. hollow column under 0.05 mm. of pressure.The following fractions were collected: 1. b.p. 115°-130° C.; 2.) b.p.130°-160° C.; combined wt. of 1 and 2=0.8 g. of 2,4-toluenediamine; 3.b.p. 160°-172° C.; 4. b.p. 172°-186° C., combined wt. of 3 and 4=3.7 g.;5. b.p. 186°-200° C., wt.=10.4 g.; 6. b.p. 200°-204° C., wt.=1.2 g.; 7.b.p. 204°-240° C., wt.=9.0 g.; residue, wt.=12.2 g.

Fractions 3 and 4 were combined and chromatographed through a column ofsilica gel (1"×14"). The column was eluted first with 400 ml. ofpetroleum ether (b.p. 35°-60° C.) followed by mixtures of 400 ml. ofpetroleum ether/methylene chloride at 85/15 parts ratio and 400 ml. at1/1 parts. Fractions were collected, evaporated, and analyzed by Nmr.The following numbered fractions were the ones yielding the significanteluted products; also shown are the solvent mixture parts ratios andproduct identity.

Chromatographic column fraction 1 (petroleum ether), wt.=1.8 g. unknownyellow oil; column fractions 9, 10 and 11 (petroleum ether/methylenechloride 85/15), wt.=1.1 g., 3-(1-indanyl-2,4-toluenediamine; columnfractions 16 and 17 (petroleum ether/methylene chloride 1/1), wt.=0.65g., 5-(1-indanyl)-2,4-toluenediamine.

Distillation fraction 7 was subjected to column chromatography followingthe same procedure described above and chromatographic column fractions10 and 11 obtained by elution with 400 ml. of petroleum ether/methylenechloride 7/3 yielded after evaporation3,5-bis(1-indanyl)-2,4-toluenediamine.

The 3-(1-indanyl)-2,4-toluenediamine obtained from chromatographiccolumn fraction 10 of distillation fractions 3 and 4 above hadcrystallized and the material was recrystallized from hot methylenechloride and petroleum ether (50/50) to provide colorless crystals, m.p.122.5°-124° C.; Nmr analysis and the following elemental analysisconfirmed the following structure in accordance with the presentinvention. ##STR12##

Calcd. for C₁₇ H₁₈ N₂ : C, 80.63%; H, 7.61%; N, 11.76%; Found: C,79.75%; H, 7.46%; N, 11.52%.

The 5-(1-indanyl)-2,4-toluenediamine obtained from chromatographiccolumn fractions 16 and 17 of distillation fractions 3 and 4 remained anoil. It was distilled under 0.05 mm. pressure of mercury, b.p. 194°-196°C. and remained a very viscous oil. Nmr analysis confirmed the followingstructure in accordance with the present invention. ##STR13##

The 3,5-bis(1-indanyl)-2,4-toluenediamine obtained from chromatographiccolumn fraction 10 of distillation fraction 7 above solidified onstanding to form a glass, fusion at 93°-97° C. Nmr and the followingelemental analysis confirmed the following structure in accordance withthe present invention. ##STR14##

Calcd. for C₂₅ H₂₆ N₂ : C, 84.70%; H, 7.39%; N, 7.91%; Found: C, 84.68%;H, 7.39%; N, 7.86%.

The reaction was repeated using the same apparatus described above using24.4 g. (0.2 mole) of 2,4-toluenediamine, 11.6 g. (0.1 mole) of indene(>90% purity described above), and 10 g. of the Zeolite catalyst. Themixture was refluxed at 200° C. for 7 hours. A small amount of indenewas still refluxing which indicated incompleteness of reaction. However,after cooling, the mixture was diluted with methylene chloride andfiltered to remove catalyst. An equal volume of petroleum ether (b.p.35°-60° C.) was added to the solution causing the precipitation of2,4-toluenediamine (12.4 g., 51% recovery dry isolated weight).

The mother liquor which still contained some toluenediamine was washed4× with 50 ml. portions of water. The organic layer was separated andsolvent removed under vacuum to yield 21.3 g. of residue. The residuewas distilled under 0.05 mm. of mercury pressure through a 5 cm. hollowcolumn and the following fractions collected and identified by Nmr andcomparison to the products isolated above.

Forerun boiling up to 35° C., wt.=1.1 g. of unreacted indene; 1. b.p.175°-184° C., wt.=0.98 g., mixture of the 3- and5-(1-indanyl)-2,4-toluenediamine; 2. b.p. 184°-187° C.; 3. b.p.187°-188° C.; 4. b.p. 188° C. constant, fractions 2 to 4, wt.=13.7 g.predominantly the 5-indanyl isomer with some of the 3-isomer; 5. b.p.188°-196° C., wt.=2.0 g. pure 5-indanyl isomer; 6. b.p. 196°-225° C.,wt.=0.98 g., 5-indanyl isomer plus a very small amount of the3,5-bis(1-indanyl)-2,4-toluenediamine; residue wt.=1 g.

The overall product yield of 17.7 g. (74.4%) was comprised of the5-(1-indanyl)-2,4-toluenediamine as the major product, with the 3-isomeras a minor component, and the bis compound in small amount.

EXAMPLE 9

Using the apparatus and procedure set forth in Example 4, a 12.2 g.sample (0.1 mole) of a mixture of 2,6- and 2,4-toluenediamine in theproportioned parts of 18.3/81.7 respectively was mixed with 59.0 g. (0.5mole) of α-methylstyrene, and 10 g. of Zeolite XZ-25. The stirredmixture was heated at 160° C. under nitrogen and aliquots were withdrawnperiodically and analyzed by HPLC. The following table of data setsforth the weight percent concentrations of the three following diaminesall in accordance with the present invention and the two isomericstarting diamines (2,6-, and 2,4-toluenediamine) as measured at threedifferent reaction intervals in the mixture. The three product diaminesare 3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamine,3-(α,α-dimethylbenzyl)-2,6-toluenediamine, and5-(α,α-dimethylbenzyl)-2,4-toluenediamine, code named 1, 2 and 3respectively.

    ______________________________________                                        Reaction                                                                      time (hrs.)                                                                            (1)       (2)     (3)     2,6- 2,4-                                  ______________________________________                                         9       2.0%      14.3%   73.5%   1.9% 8.3%                                  25       7.7%      9.4%    75.4%   0.4% 6.9%                                  45       10.2%     8.9%    75.1%   0.4% 5.4%                                  ______________________________________                                    

The reaction mixture was worked-up identically to the procedure setforth in Example 4. Distillation of the crude reaction product underhigh vacuum (described in Example 4) provided the following productdistribution and overall yield of materials: 0.0104 mole of dibenzylatedproduct (1), 0.0752 mole of the mixture of the monobenzylated products(2) and (3) to give an overall yield of 75.6%. HPLC analysis showed theweight percent distribution of (1), (2), and (3) in the isolatedproducts based on their combined weights to be 10.5%, 10.1%, and 79.4%respectively.

EXAMPLE 10

A 250 ml 3-necked flask equipped with a magnetic stirrer, a thermometer,a reflux condenser (equipped with a nitrogen inlet tube), and a shortpath distillation head with condenser, receiver and a nitrogen outlet,was charged with a mixture of 9.76 g. (0.08 mole) of 2,4-toluenediamineand 2.44 g. (0.02 mole) of 2,6-toluenediamine, 59.1 g. (0.5 mole) ofα-methylstyrene, 0.055 g. of hydroquinone, and 1.9 g. (0.01 mole) ofp-toluene sulfonic acid monohydrate.

The system was flushed with nitrogen and then under a slow stream ofnitrogen and during continual stirring the reaction mixture was heatedrapidly to 160° C. Water of hydration from the sulfonic acid wasreleased starting at about 120° C., carried from the reaction flask withthe nitrogen stream, and collected in the receiver with a small amountof α-methylstyrene. When the water generation stopped, the nitrogenoutlet was closed and the system maintained under a slight positivepressure of nitrogen by means of a gas bubbler.

Aliquot samples were withdrawn from the reaction mixture periodically(circa every hour) and analyzed by HPLC (column material was μ-Porasiland the elutant was a mixture of acetonitrile and 1,2-dichloroethane ina volume/volume ratio of 490/3000.

When conversion of the diaminotoluene reached about 75 percent, in about3 hours, the weight percent concentrations of the starting amines andproducts was as follows:

    ______________________________________                                        2,4-toluenediamine =      13.7%                                               2,6-toluenediamine =      7.2%                                                5-(α,α-dimethylbenzyl)-2,4-toluenediamine =                                                 63.0%                                               3-(α,α-dimethylbenzyl)-2,6-toluenediamine =                                                 14.5%                                               3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamine                                              1.6%                                                ______________________________________                                    

The reaction was stopped at this point and cooled rapidly (within 0.5hour) first by forced air and then by cold water bath to roomtemperature (circa 20° C.) during continuous stirring. As the reactionmixture cooled, p-toluene sulfonic acid crystallized out gradually asthe salt of a toluenediamine.

After 2 hours at room temperature, 30 ml. of methylene chloride wasadded to the reaction mixture which was then stirred for 1 hour. Themixture was filtered and 2.83 g. (97% yield) of the 1:1 salt ofp-toluene sulfonic acid and 2,4-toluenediamine was obtained. Thesulfonic acid salt which was collected, was washed twice with 15 ml.portions of methylene chloride.

The filtrate and washings were combined and the small amount of residualacid in the solution was neutralized by bubbling a slow stream ofanhydrous ammonia into the solution with stirring until the pH reached 8to 9. The sulfonic acid precipitated as ammonium p-toluene sulfonatewhich was removed by filtration. Methylene chloride and ammonia wereremoved from the mixture by rotary evaporation under aspiratory vacuum(circa 20-30 mm of mercury pressure) at a temperature of up to about 40°C.

The excess α-methylstyrene was distilled at a head temperature of 70° to80° C. under a pressure of about 23 mm of mercury and the residue wasdistilled under 0.03 mm of mercury and the following fractions werecollected and identified by NMR:#1. b.p. 80°-155° C., wt.=3.1 g. ofcolorless distillate which crystallized at room temperature andcontained 0.3 g. dimer of α-methylstyrene and 2.8 g. of a mixture of2,4-toluenediamine, 2,6-toluenediamine,5-(α,α-dimethylbenzyl)-2,4-toluenediamine, and3-(α,α-dimethylbenzyl)-2,6-toluenediamine in the molar percentproportions of 54.9%, 23.1%, 17.8%, and 4.2% respectively; #2. b.p.155°-175° C., wt.=15.0 g. yellow glass which was a mixture of5-(α,α-dimethylbenzyl)-2,4-toluenediamine,3-(α,α-dimethylbenzyl)-2,6-toluenediamine, and3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamine in the molar proportionsof 81.2%, 17.9%, and 0.9% respectively, and 0.1 g. of oligomers ofα-methylstyrene as well as a trace of some N-alkylated side-products;#3. b.p. 175°-182° C., wt.=1.1 g. of orange colored distillate which wasa mixture of 0.7 g. of 3,5-bis(α,α-dimethylbenzyl)-2,6-toluenediamineand 0.4 g. of oligomers of α-methylstyrene. A residue of 0.3 g. of blacktar remained in the stillpot.

Fraction #2 was essentially a pure mixture of three alkylatedphenylenediamines in accordance with the present invention. Thecompletely pure crystalline mixture of the three products is obtainedfrom the glass by recrystallization from toluene and petroleum ether.The total yield of alkylated products based on converted toluene diaminestarting material was 87%.

EXAMPLE 11

The following two molded polyurethane-polyurea polymers A and B wereprepared by a hand-mix technique. Polymer A was in accordance with thepresent invention while Polymer B was prepared in accordance with theprior art.

The molded polymers were prepared by reacting the ingredients in theproportions of parts by weight set forth in Table I, as an A componentwith a B component. Both components were mixed at high speed at roomtemperature (about 20° C.) in quart tubs using a drill press motorequipped with a Conn 3" blade. The ingredients were mixed for about 5 to6 seconds and then immediately poured into a metal mold measuring77/8"×77/8"×1/4" at 150° F. which mold was coated with a mold releaseagent (XMR-136 supplied by Chem-Trend Inc., Howell, Mich. 48843). Thedemold time was about 2 minutes for A and about 4 minutes for B. Bothsamples were post-cured for 1 hour at 250° F. and then subjected to thetest procedures set forth in Table I.

The sample A in accordance with the present invention exhibited goodphysical and thermal properties. These properties, even if allowance ismade for a density difference, are for the most part significantlybetter than those of the prior art sample B, particularly in regard tothermal stability.

                  TABLE I                                                         ______________________________________                                                     Sample                                                                        A         B                                                      ______________________________________                                        Ingredients (pts. by wt.)                                                     A Component:   57.9 (0.4008 eq.)                                                                         78.44 (0.5432 eq.)                                 Polyisocyanate 1.sup.1                                                        B Component:                                                                  E 2105.sup.2   100 (0.1 eq.)                                                                             100 (0.1 eq.)                                      5-(α,α-dimethylbenzyl)-                                                            35 (0.2892 eq.)                                                                         --                                                 2,4-toluenediamine                                                            Ethylene glycol                                                                              --          13.25 (0.4274 eq.)                                 Dibutyl tin dilaurate                                                                        0.125       0.125                                              NCO/OH Index   1.03        1.03                                               [A]/[B] Ratio  0.429       0.693                                              Catalyst (total wt. %)                                                                        0.064%      0.065%                                            % Hard segment   40.7%       40.3%                                            Properties:                                                                   Density (g./cc)                                                                              1.078       0.914                                              Shore D hardness                                                                              55          35                                                Tensile str. (psi)                                                                           2720        1440                                               Elongation at break (%)                                                                       198         292                                               Flexural modulus (psi)                                                                       32,809      6201                                               Flexural strength (psi)                                                                      1954         434                                               Heat sag, inches.sup.3                                                                       0.085       0.32                                               at 250° F./1 hr.                                                       ______________________________________                                         Footnotes to Table I                                                          .sup.1 The polyisocyanate is a liquefied methylenebis(phenyl isocyanate)      containing uretoneimine group, I.E. = 144.4.                                  .sup.2 E 2105 is Thanol E 2105 ethyleneoxide capped polypropyleneoxy          glycol, 45% ethylene oxide content by wt., 2000 M.W.; supplied by Texaco      Chem. Corp., Bellaire, Texas.                                                 .sup.3 Heat sag is determined in accordance with Test CTZ006AA of the         Chevrolet Div. of General Motors Corp., Flint, Mich. It is the amount, in     inches, that a 1 inch wide sample with a 4 inch long unsupported length       droops under its own weight when h eld at one end in a horizontal positio     under the specified conditions of time and temperature.                  

I claim:
 1. A m-phenylenediamine having (a) at least one, and not morethan two, of the positions ortho to the amino groups substituted by amember selected from benzyl groups having the formulae: ##STR15##wherein R₁ is selected from the class consisting of hydrogen and loweralkyl, R₂ is lower alkyl, C_(n) H_(2n) is alkylene having from 2 to 5carbon atoms in the chain, R is an inert substituent selected from thegroup consisting of alkyl, aralkyl, aryl, cycloalkyl, halogen, nitro,alkoxy, alkylmercapto, and cyano, n is an integer from 0 to 5, and m isan integer from 0 to 4; and (b) a member selected from the groupconsisting of hydrogen and lower alkyl attached to the nuclear carbonatoms ortho to the amino groups which do not carry one of said benzylgroups.
 2. A m-phenylenediamine according to claim 1 which isadditionally substituted by hydrocarbyl on the nuclear carbon atom whichis in the meta position with respect to the two amino groups.
 3. Am-phenylenediamine having (a) at least one, and not more than two, ofthe positions ortho to the amino groups substituted by a benzyl grouphaving the formula ##STR16## wherein R₁ is selected from the classconsisting of hydrogen and lower alkyl and R₂ is lower alkyl; and (b) amember selected from the group consisting of hydrogen and lower alkylattached to the nuclear carbon atoms ortho to the amino groups which donot carry one of said benzyl groups.
 4. A diamine according to claim 3having the formula ##STR17##
 5. A diamine according to claim 3 havingthe formula ##STR18##
 6. A diamine according to claim 3 having theformula ##STR19##
 7. A diamine mixture according to claim 3comprising(a) from about 70 to about 95 percent by weight of ##STR20##and (b) from about 30 to about 5 percent by weight of ##STR21## based onthe combined weight of (a) and (b).
 8. A diamine according to claim 3having the formula ##STR22##
 9. A diamine according to claim 3 havingthe formula ##STR23##
 10. A diamine according to claim 3 having theformula ##STR24##
 11. A diamine according to claim 3 having the formula##STR25##
 12. A diamine according to claim 1 having the formula##STR26##